The study of photochemical methods to effect chemical transformations has centered on photoextrusion of small molecules, particularly SO2 from sulfones and H2O from oxazines. In the first case, new carbon-carbon bonds are generated from a relatively readily available functional group. The mechanism by which extrusion takes place is largely dependent on the structural parameters of the sulfone substrate. This process has been successfully applied to the synthesis of strained hydrocarbons, e.g., cyclophanes. The H2O extrusion from oxazines represents another case where ready access to the reactant provides a convenient entry to more difficulty accessible photoproducts, here pyrroles. The pyrrole substitution pattern can be controlled by proper choice of dienes in the cycloaddition reactions with nitrosoaromatics to give the substituted oxazines. Thus, a general route to substituted pyrroles is envisaged. Several additional functional groups have also been examined in expectation of synthetic applications of these photochemically initiated fragmentation reactions.